arXiv subjects

Nicolas Douguet

Publications and source records attributed to Nicolas Douguet.

At least 19 recordsLinked to original sources

arXiv2025

Multi-messenger tracking of coherence loss during bond breaking

Coupled electronic and nuclear motions govern chemical reactions, yet disentangling their interplay during bond rupture remains challenging. Here we follow the light-induced fragmentation of Br$_2$ using a coincidence-based multi-messenger approach. A UV pulse prepares the dissociative state, and strong-field ionization probes the evolving system. Coincident measurement of three-dimensional photoion and photoelectron momenta provides real-time access to both the instantaneous internuclear separation and the accompanying reorganization of the electronic structure, allowing us to determine the timescale of bond breaking. We find that electronic rearrangement concludes well before the nuclei reach the bond-breaking distance, revealing a hierarchy imposed by electron-nuclear coupling. Supported by semiclassical modelling, the results show that the stretched Br$_2$ molecule behaves as a two-centre interferometer in which the loss of coherence between atomic centres encodes the coupled evolution of electrons and nuclei. Our work establishes a general framework for imaging ultrafast electron-nuclear dynamics in molecules.

physics.chem-ph↗

arXiv2025

Generation of Bright and Controllable Isolated Attosecond X-Ray Pulses from Synchronized Mid-Infrared and Ultra-short Ultraviolet Laser Fields

We investigate, by solving the time-dependent Schrödinger equation in the single-active-electron approximation in helium, a two-color scheme for tabletop high-order harmonic generation (HHG) that combines a mid-infrared (MIR) driving field with an ultrashort ultraviolet (UV) pulse that could be generated via resonant dispersive wave emission in gas-filled hollow-core fibers. This configuration enables the generation of bright, isolated, and tunable attosecond X-ray pulses. In contrast to single-color driving schemes, which suffer from low conversion efficiency, unfavorable wavelength scaling, and limited spectral control, the MIR+UV approach provides a practical and controllable route for advancing tabletop ultrafast spectroscopy and real-time molecular imaging within current experimental capabilities.

physics.optics↗

arXiv2025

Hybrid basis and multi-center grid method for strong-field processes

We present a time-dependent framework that combines a hybrid Gaussian-FEDVR basis with a multicenter grid to simulate strong-field and attosecond dynamics in atoms and molecules. The method incorporates the construction of the orthonormal hybrid basis, the evaluation of electronic integrals, a unitary time-propagation scheme, and the extraction of optical and photoelectron observables. Its accuracy and robustness are benchmarked on one-electron systems such as atomic hydrogen and the dihydrogen cation ($\text{H}_{2}^{+}$) through comparisons with essentially-exact reference resutls for bound-state energies, high-harmonic generation spcetra, photoionization cross sections, and photoelectron momentum distributions. This work establishes the groundwork for its integration with quantum-chemistry methods, which are already operational but will be detailed in future work, thereby enabling ab initio simulations of correlated polyatomic systems in intense ultrafast laser fields.

physics.atom-ph↗

arXiv2025

Dichroic Electron Emission Patterns from Oriented Helium Ions

We report a joint experimental and theoretical study using a combination of polarization-controlled free-electron-laser (FEL) and near-infra\-red (NIR) pulses in a synchronized two-color photo\-ionization scheme. Excited He$^+$ ions, created by extreme ultraviolet (XUV) circularly polarized radiation from the XUV-FEL FERMI in the oriented $3p\, (m\!=\!+1)$ state, are exposed to circularly polarized 784-nm NIR radiation with peak intensities from $10^{12}\,\rm W/cm^2$ to $\rm 10^{13}\,W/cm^2$. The angular distribution of the ejected electrons exhibit a strong dichroism depending on the NIR intensity. While the co-rotating case is defined by a single path, for the counter-rotating case, there are two dominant pathways whose relative strength and phase difference are determined.

physics.atom-ph↗

arXiv2024

Circular Dichroism in Multiphoton Ionization of Resonantly Excited Helium Ions near Channel Closing

The circular dichroism (CD) of photoelectrons generated by near-infrared (NIR) laser pulses using multiphoton ionization of excited He$^+$ ions in the 3p(m=+1) state. The ions were prepared by circularly polarized extreme ultraviolet (XUV) pulses. For circularly polarized NIR pulses co- and counter-rotating relative to the polarization of the XUV pulse, a complex variation of the CD is observed as a result of intensity- and polarization-dependent Freeman resonances, with and without additional dichroic AC-Stark shifts. The experimental results are compared with numerical solutions of the time-dependent Schrödinger equation to identify and interpret the pronounced variation of the experimentally observed CD.

physics.atom-ph↗

arXiv2024

Strong-Field Ionization Phenomena Revealed by Quantum Trajectories

We investigate the photoionization dynamics of atoms subjected to intense, ultrashort laser pulses through the use of quantum trajectories. This method provides a unique and consistent framework for examining electron dynamics within a time-dependent potential barrier. Our findings demonstrate that quantum trajectories offer additional insights into several key aspects of strong-field ionization, including the transition between ionization regimes, non-adiabatic effects under the barrier, the impact of the shape of the electronic potential, and the efficiency of over-the-barrier ionization.

physics.atom-ph↗

arXiv2023

Opportunities for Gas-Phase Science at Short-Wavelength Free-Electron Lasers with Undulator-Based Polarization Control

Free-electron lasers (FELs) are the world's most brilliant light sources with rapidly evolving technological capabilities in terms of ultrabright and ultrashort pulses over a large range of accessible photon energies. Their revolutionary and innovative developments have opened new fields of science regarding nonlinear light-matter interaction, the investigation of ultrafast processes from specific observer sites, and approaches to imaging matter with atomic resolution. A core aspect of FEL science is the study of isolated and prototypical systems in the gas phase with the possibility of addressing well-defined electronic transitions or particular atomic sites in molecules. Notably for polarization-controlled short-wavelength FELs, the gas phase offers new avenues for investigations of nonlinear and ultrafast phenomena in spin orientated systems, for decoding the function of the chiral building blocks of life as well as steering reactions and particle emission dynamics in otherwise inaccessible ways. This roadmap comprises descriptions of technological capabilities of facilities worldwide, innovative diagnostics and instrumentation, as well as recent scientific highlights, novel methodology and mathematical modeling. The experimental and theoretical landscape of using polarization controllable FELs for dichroic light-matter interaction in the gas phase will be discussed and comprehensively outlined to stimulate and strengthen global collaborative efforts of all disciplines.

physics.atom-ph↗

arXiv2022

High-Harmonic Generation in the Water Window from mid-IR Laser Sources

We investigate the harmonic response of neon atoms to mid-IR laser fields (2000-3000nm) using a single-active electron (SAE) model and the fully ab initio all-electron R-Matrix with Time-dependence (RMT) method. The laser peak intensity and wavelength are varied to find suitable parameters for high-harmonic imaging in the water window. Comparison of the SAE and RMT results shows qualitative agreement between them as well as parameters such as the cutoff frequency predicted by the classical three-step model. However, there are significant differences in the details, particularly in the predicted conversion efficiency. These details indicate the possible importance of multi-electron effects, as well as a strong sensitivity of quantitative predictions on specific aspects of the numerical model.

physics.atom-ph↗

arXiv2022

Photoelectron momentum distributions in the strong-field ionization of atomic hydrogen by few-cycle elliptically polarized optical pulses

We investigate the strong-field ionization of atomic hydrogen in a few-cycle elliptically polarized infrared pulse by solving the time-dependent Schrödinger equation. The dependence of the photoelectron momentum distribution on the pulse intensity, ellipticity, length, envelope, and carrier envelope phase is analyzed. In particular, we explain the variation of the electron offset angle with asymptotic electron energy through the combined action of the field and the Coulomb potential, and demonstrate that low-ellipticity pulses make it possible to access the electron release time.

physics.atom-ph↗

arXiv2021

Attosecond Intramolecular-Scattering and Vibronic Delay

The photoionization of the CO molecule from the C$-1s$ orbital does not obey the Franck-Condon approximation, as a consequence of the nuclear recoil that accompanies the direct emission and intra-molecular scattering of the photoelectron. We use an analytical model to investigate the temporal signature of the entangled nuclear and electronic motion in this process. We show that the photoelectron emission delay can be decomposed into its localization and resonant-confinement components. Finally, photoionization by a broadband soft-x-ray pulse results in a coherent vibrational ionic state with a tunable delay with respect to the classical sudden-photoemission limit.

physics.atom-ph↗

arXiv2021

A Multi-Center Quadrature Scheme for the Molecular Continuum

A common way to evaluate electronic integrals for polyatomic molecules is to use Becke's partitioning scheme [J. Chem. Phys.88, 2547 (1988)] in conjunction with overlapping grids centered at each atomic site. The Becke scheme was designed for integrands that fall off rapidly at large distances, such as those approximating bound electronic states. When applied to states in the electronic continuum, however, Becke scheme exhibits slow convergence and it is highly redundant. Here, we present a modified version of Becke scheme that is applicable to functions of the electronic continuum, such as those involved in molecular photoionization and electron-molecule scattering, and which ensures convergence and efficiency comparable to those realized in the calculation of bound states. In this modified scheme, the atomic weights already present in Becke's partition are smoothly switched off within a range of few bond lengths from their respective nuclei, and complemented by an asymptotically unitary weight. The atomic integrals are evaluated on small spherical grids, centered on each atom, with size commensurate to the support of the corresponding atomic weight. The residual integral of the interstitial and long-range region is evaluated with a central master grid. The accuracy of the method is demonstrated by evaluating integrals involving integrands containing Gaussian Type Orbitals and Yukawa potentials, on the atomic sites, as well as spherical Bessel functions centered on the master grid. These functions are representative of those encountered in realistic electron-scattering and photoionization calculations in polyatomic molecules.

physics.chem-ph↗

arXiv2021

Towards the complete phase profiling of attosecond wave packets

Realistic attosecond wave packets have complex profiles that, in dispersive conditions, rapidly broaden or split into multiple components. Such behaviors are encoded in sharp features of the wave packet spectral phase. Here, we exploit the quantum beating between one- and two-photon transitions in an attosecond photoionization experiment to measure the photoelectron spectral phase continuously across a broad energy range. Supported by numerical simulations, we demonstrate that this experimental technique is able to reconstruct sharp fine-scale features of the spectral phase, continuously as a function of energy and across the full spectral range of the pulse train, thus beyond the capabilities of existing attosecond spectroscopies. In a proof-of-principle experiment, we retrieve the periodic modulations of the spectral phase of an attosecond pulse train due to the individual chirp of each harmonic.

physics.atom-ph↗

arXiv2020

Decomposition of the transition phase in multi-sideband RABBITT schemes

Reconstruction of Attosecond Beating By Interference of Two-photon Transitions (RABBITT) is a technique that can be used to determine the phases of atomic transition elements in photoionization processes. In the traditional RABBITT scheme, the so-called "asymptotic approximation" considers the measured phase as a sum of the Wigner phase linked to a single-photon ionization process and the continuum-continuum (cc) phase associated with further single-photon transitions in the continuum. In this paper, we explore the possibility of extending the asymptotic approximation to multi-sideband RABBITT schemes. The predictions from this approximation are then compared with results obtained by an {\it ab initio} calculation based on solving the time-dependent Schrödinger equation for atomic hydrogen.

quant-ph↗

arXiv2020

Photoelectron spectroscopy of laser-dressed atomic helium

Photoelectron emission from excited states of laser-dressed atomic helium is analyzed with respect to laser intensity-dependent excitation energy shifts and angular distributions. In the two-color XUV (exteme ultra\-violet) -- IR (infrared) measurement, the XUV photon energy is scanned between \SI{20.4}{\electronvolt} and the ionization threshold at \SI{24.6}{\electronvolt}, revealing electric dipole-forbidden transitions for a temporally overlapping IR pulse ($\sim\!\SI{e12}{\watt\per \centi\meter\squared}$). The interpretation of the experimental results is supported by numerically solving the time-dependent Schrödinger equation in a single-active-electron approximation.

physics.atom-ph↗

arXiv2020

Ellipticity Dependence of Excitation and Ionization of Argon Atoms by Short-Pulse Infrared Radiation

When atoms or molecules are exposed to strong short-pulse infrared radiation, ionization as well as "frustrated tunneling ionization" (FTI) can occur, in which a portion of the almost ionized electrons recombine into the initial ground or an excited bound state. We analyze the ellipticity dependence of the relative signals that are predicted in a single-active electron approximation (SAE), the validity of which is checked against a parameter-free multi-electron \hbox{$R$-matrix} (close-coupling) with time dependence approach. We find good agreement between the results from both models, thereby providing confidence in the SAE model potential to treat the process of interest. Comparison of the relative excitation probabilities found in our numerical calculations with the predictions of Landsman {\it et al.}\ (New Journal of Physics {\bf 15} (2013) 013001) and Zhao {\it et al.}\ (Optics Express {\bf 27} (2019) 21689) reveals good agreement with the former for short pulses. For longer pulses, the ellipticity dependence becomes wider than that obtained from the Landsman {\it et al.} formula, but we do not obtain the increase compared to linearly polarized radiation predicted by Zhao {\it et al.}

physics.atom-ph↗

arXiv2020

Observation of Dynamic Stark Resonances in Strong-Field Excitation

We investigate AC Stark-shifted resonances in argon with ultrashort near-infrared pulses. Using 30 fs pulses we observe periodic enhancements of the excitation yield in the intensity regions corresponding to the absorption of 13 and 14 photons. By reducing the pulse duration to 6 fs with only a few optical cycles, we also demonstrate that the enhancements are significantly reduced beyond what is measurable in the experiment. Comparing these to numerical predictions, which are in quantitative agreement with experimental results, we find that even though the quantum-state distribution can be broad, the enhancements are largely due to efficient population of a select few AC Stark-shifted resonant states rather than the closing of an ionization channel. Because these resonances are dependent on the frequency and intensity of the laser field, the broad bandwidth of the 6 fs pulses means that the resonance condition is fulfilled across a large range of intensities. This is further exaggerated by volume-averaging effects, resulting in excitation of the $5g$ state at almost all intensities and reducing the apparent magnitude of the enhancements. For 30 fs pulses, volume averaging also broadens the quantum state distribution but the enhancements are still large enough to survive. In this case, selectivity of excitation to a single state is reduced below 25% of the relative population. However, an analysis of TDSE simulations indicates that excitation of up to 60% into a single state is possible if volume averaging can be eliminated and the intensity can be precisely controlled.

physics.atom-ph↗

arXiv2019

Time delays from one-photon transitions in the continuum

Attosecond photoionisation time delays reveal information about the potential energy landscape an outgoing electron wavepacket probes upon ionisation. In this study we experimentally quantify, for the first time, the dependence of the time delay on the angular momentum of the liberated photoelectrons. For this purpose, electron quantum-path interference spectra have been resolved in energy and angle using a two-color attosecond pump-probe photoionisation experiment in helium. A fitting procedure of the angle-dependent interference pattern allows us to disentangle the relative phase of all four quantum pathways that are known to contribute to the final photoelectron signal. In particular, we resolve the dependence on the angular momentum of the delay of one-photon transitions between continuum states, which is an essential and universal contribution to the total photoionization delay observed in attosecond pump-probe measurements. For such continuum-continuum transitions, we measure a delay between outgoing s- and d-electrons as large as 12 as close to the ionisation threshold in helium. Both single-active-electron and first-principles ab initio simulations confirm this observation for helium and hydrogen, demonstrating the universality of the observed delays.

physics.atom-ph↗

arXiv2019

Circular holographic ionization-phase meter

We propose an attosecond XUV-pump IR-probe photoionization protocol that employs pairs of counter-rotating consecutive harmonics and angularly resolved photoelectron detection, thereby providing direct measurement of ionization phases. The present method, which we call circular holographic ionization-phase meter (CHIP), gives also access to the phase of photoemission amplitudes of even-parity continuum states from a single time-delay measurement, since the relative phase of one- and two-photon ionization pathways is imprinted in the photoemission anisotropy. The method is illustrated with \emph{ab initio} simulations of photoionization via autoionizing resonances in helium. The rapid phase excursion in the transition amplitude to both the dipole-allowed $(2s2p)^1$P$^{\rm o}$ and the dipole-forbidden $(2p^2)^1$D$^{\rm e}$ states are faithfully reproduced.

physics.atom-ph↗